CN103086849B - Liquid crystal compound and composition thereof - Google Patents
Liquid crystal compound and composition thereof Download PDFInfo
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- CN103086849B CN103086849B CN201210553833.1A CN201210553833A CN103086849B CN 103086849 B CN103086849 B CN 103086849B CN 201210553833 A CN201210553833 A CN 201210553833A CN 103086849 B CN103086849 B CN 103086849B
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- 0 *C(CC1)COC1C(CC1)CC=C1C(C1)=CC(F)=C(*C(C2)=CCC(C(CC3)CCC3(F)F)C2F)C1F Chemical compound *C(CC1)COC1C(CC1)CC=C1C(C1)=CC(F)=C(*C(C2)=CCC(C(CC3)CCC3(F)F)C2F)C1F 0.000 description 2
- TXOMTNSBAZKHPZ-UHFFFAOYSA-N CC(C)(CC1)CCC1c(c(C)c1)c(C)cc1N=O Chemical compound CC(C)(CC1)CCC1c(c(C)c1)c(C)cc1N=O TXOMTNSBAZKHPZ-UHFFFAOYSA-N 0.000 description 1
- FMUDDYBZEXAOFL-UHFFFAOYSA-N NC1C=CCC=C1 Chemical compound NC1C=CCC=C1 FMUDDYBZEXAOFL-UHFFFAOYSA-N 0.000 description 1
- SIVMZZJERMKGKQ-UHFFFAOYSA-N O=C(C1=CCCCC1)C(C=C(C1C(CC2)=CCC2(F)F)F)=CC1F Chemical compound O=C(C1=CCCCC1)C(C=C(C1C(CC2)=CCC2(F)F)F)=CC1F SIVMZZJERMKGKQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a liquid crystal compound and a composition thereof. The compound simultaneously has the structure with a difluoro methyl ether bridge bond and 4,4-difluoro cyclohexane (or is terminated with halogenated cyclohexene). The compound has the characteristics that the structure and the property are stable, the intersolubility is good, the ultraviolet resistance is good, the charge retention rate is high and the dielectric anisotropy is large. After the liquid crystal compound is applied to the liquid crystal composition, a threshold voltage can be reduced, the Delta n value of the system is adjusted, and the comprehensive performance of the liquid crystal composition can be enhanced or improved. The liquid crystal compound is particularly applicable to TN, IPS, FFS, ADS-TFT modes and other similar display modes.
Description
Technical field
The present invention relates to liquid crystal material field.Specifically, a kind of liquid crystalline cpd and preparation method thereof and application is related to.
Background technology
1888, Austria botanist Friedrich Reinitzer finds liquid crystal, and after this, the research and apply of liquid crystal develops rapidly, especially, after within 1971, having found twisted nematic liquid crystal field-effect together with W.Helfrich with M.Schadt, lcd technology is achieved.
Liquid-crystal display has passive matrix [also known as passive-matrix (Passive Matrix, PM) or simple matrix] and active matrix [also known as active-matrix (Active Matrix, AM)] two kinds of type of drive.Active matrix liquid crystal display can two-terminal active matrix and the large class of three terminal active matrixs two according to the kind of active part.Two end active mode techniques are relatively simple, but the difference that picture quality is more active than three ends, closely superseded at present.Three end active matrixs are based on Thin Film Transistor (TFT) (Thin Film Transistor, TFT).TFT-LCD is the Typical Representative of active matrix liquid crystal display, and its research is the most active, with fastest developing speed, application increases also the rapidest.TFT-LCD is obtained for good application on the display equipments such as mobile phone, desktop computer, notebook computer, LCD TV and pick up camera.
At present, TFT-LCD product technology is ripe, successfully solves the technical barriers such as visual angle, resolving power, fullness of shade and brightness, its display performance close to or exceed CRT monitor.Large size and small-medium size TFT-LCD indicating meter occupy the dominant position of flat-panel monitor gradually in respective field.But because of the restriction by liquid crystal material itself, it is fast not that TFT-LCD still also exists response, and voltage is low not, the high not many defects of electric charge conservation rate.
Within 1989, Merck KGaA company is disclosed the liquid-crystal composition with difluoro methyl ether bridged bond in patent US5045229, but does not apply in liquid-crystal composition.Until middle nineteen nineties in last century Japan Chisso Corporation just develop this compounds (CN1158602) that really can apply in liquid-crystal composition.Such compound dissolution performance increases; Moment of dipole strengthens, and cause its dielectric anisotropy comparatively large, be conducive to the reduction of saturation voltage, such material has good application prospect in field of liquid crystal display.
Merck KGaA company in 1994 in patent DE4430668 to having 4, the synthesis of 4-difluorocyclohex alkyl structure liquid crystalline cpd is carried out open, and within 1987, large Japanese ink company of Japan carries out open to the synthesis that end has halo cyclohexene liquid crystalline cpd in patent JP63238030.Such compound dissolution performance increases, and also has certain development prospect.But for now, still await proposing the liquid crystalline cpd of novel excellent performance and composition thereof to obtain higher-quality liquid crystal indicator.
Summary of the invention
In order to solve the problem, the invention provides a kind of novel liquid crystalline cpd.This compounds has difluoro methyl ether bridged bond and 4,4-difluorocyclohex alkane (or end has halo tetrahydrobenzene) structure simultaneously.Described compound structure, stable in properties, have mutual solubility good, and uvioresistant performance is good, and electric charge conservation rate is high, the feature that dielectric anisotropy is large.After being applied to liquid-crystal composition, can threshold voltage be reduced, the Δ n numerical value of regulation system, and can improve or improve the over-all properties of liquid-crystal composition.Especially TN, IPS, FFS, ADS-TFT pattern and similar display format is suitable for.
For achieving the above object, the present invention specifically adopts following technical scheme:
A kind of liquid crystalline cpd, described liquid crystalline cpd has such as formula the structure shown in Ι or II:
Wherein:
R represents C
1~ C
12alkyl, wherein part CH
2group can be replaced by-C ≡ C-,-CF=CF-,-CF=CH-,-CH=CF-,-COO-or-O-separately independently of one another;
A
1, A
2represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene independently of one another, wherein Isosorbide-5-Nitrae-cyclohexylidene is not substituted or wherein 1 ~ 2 CH
2isosorbide-5-Nitrae-cyclohexylidene that group is replaced by Sauerstoffatom; Isosorbide-5-Nitrae-phenylene is not substituted or Isosorbide-5-Nitrae-phenylene that 1 ~ 4 hydrogen atom is replaced by fluorine atoms;
A
3isosorbide-5-Nitrae-phenylene that expression is not substituted or 1 ~ 4 hydrogen atom is replaced by fluorine atoms;
Z
1, Z
2represent singly-bound ,-CH independently of one another
2cH
2-,-CF
2o-,-OCF
2-,-CH
2o-,-OCH
2-,-CH
2cF
2-,-CF
2cH
2-,-CH
2cHF-,-CHFCH
2-,-COO-,-OOC-,-CF=CF-,-CH=CH-or-C ≡ C-;
M represent 1,2 or 3, n represent 0,1 or 2.
Further, in the preferred above-mentioned general formula of the present invention:
R represents C
1~ C
7alkyl, wherein part CH
2group can separately independently of one another by-C ≡ C-,-CF=CF-,-CF=CH-,-CH=CF-;
A
1, A
2represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene independently of one another, wherein Isosorbide-5-Nitrae-cyclohexylidene is not substituted or wherein 1 CH
2isosorbide-5-Nitrae-cyclohexylidene that group is replaced by Sauerstoffatom, Isosorbide-5-Nitrae-phenylene is not substituted or Isosorbide-5-Nitrae-phenylene that 1 ~ 4 hydrogen atom is replaced by fluorine atoms;
A
3represent Isosorbide-5-Nitrae-phenylene that 1 ~ 4 hydrogen atom is replaced by fluorine atoms;
Z
1, Z
2represent singly-bound independently of one another;
M represent 2 or 3, n represent 0.
The preferred structural formula of the present invention is I 1 to I 4 and II 1 to II 4, but is not limited only to this structural formula:
Wherein, R represents C
1~ C
5alkyl, wherein part CH
2group can be replaced by-C ≡ C-,-CF=CF-,-CF=CH-or-CH=CF-separately independently of one another.
Through experimental test, above-mentioned liquid crystalline cpd structure, stable in properties, prove that it has the advantages that mutual solubility is good, uvioresistant performance is good, electric charge conservation rate is high and dielectric anisotropy is large.
The second object of the present invention is the preparation method providing above-mentioned liquid crystalline cpd, and for realizing the second object, the present invention adopts following technical scheme:
The preparation method of above-mentioned liquid crystalline cpd, comprises the steps:
(1)
through the lithium reagent that n-Butyl Lithium activation is formed, generate intermediate ethanol with 4,4-difluorocyclohex reactive ketone
dehydration of alcohols obtains compd A
(2) compd A obtains compd B through shortening
(3) compd B and corresponding salt
reaction, obtains target compound Ι;
(4) compound Ι sloughs a hydrogen fluoride under basic catalyst effect, obtains target compound II.
Wherein, in described step (1),
the mol ratio of n-Butyl Lithium and 4,4-difluoro-cyclohexanone is 1 ~ 1.1:1.1 ~ 1.5:1, and dehydration catalyst is tosic acid.
In described step (2), described shortening is with palladium carbon for catalyzer, and the consumption of catalyzer is 5% ~ 10% of compd A quality, under room temperature condition, carries out shortening to compd A.
In described step (3), temperature of reaction is-80 ~-85 DEG C, and the mol ratio of compd B and corresponding salt is 1 ~ 1.2:1.
In described step (4), described basic catalyst is potassium tert.-butoxide or potassium hydroxide, and the reaction times is 8 ~ 10 hours.
More preferably:
In the step (1) of preparation method of the present invention,
the mol ratio of n-Butyl Lithium and 4,4-difluoro-cyclohexanone is 1:1:1.
In the step (2) of described preparation method, described shortening is with palladium carbon for catalyzer, and the consumption of catalyzer is 8% of compd A quality, under room temperature condition, to compd A shortening.
In the step (3) of described preparation method, temperature of reaction is-80 ~-85 DEG C, and the mol ratio of compd B and corresponding salt is 1:1.
In the step (4) of described preparation method, described basic catalyst is potassium tert.-butoxide, and the reaction times is 10 hours.
The third object of the present invention is to provide a kind of liquid-crystal composition containing above-mentioned liquid crystalline cpd.Wherein, the consumption of preferred above-mentioned liquid crystalline cpd is the 1-70% of liquid-crystal composition, preferred 5-50%, more preferably 20-25%.
In above-mentioned liquid-crystal composition, the those skilled in the art that are defined as of other compositional selectings and consumption thereof grasped.The present invention is not particularly limited this.But predictably, add above-mentioned liquid crystalline cpd and namely can reduce threshold voltage, the Δ n numerical value of regulation system, and can improve or improve the over-all properties of liquid-crystal composition.
In addition, the present invention also further claimed above-mentioned liquid crystalline cpd is manufacturing the application in display unit, is especially suitable for TN, IPS, FFS, ADS – TFT pattern and similar display format.
Adopt technique scheme, novel liquid crystal compound provided by the present invention has stable in properties, and mutual solubility is good, uvioresistant performance is good, the feature that dielectric anisotropy is large, described compound can apply in liquid-crystal composition, improves or improve the over-all properties of liquid-crystal composition.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.Prepare liquid crystalline cpd of the present invention, methodology of organic synthesis well known in the art can be used to carry out highway route design and synthesis.The present invention to preparation method's citing of described liquid crystalline cpd as shown in the Examples, but is not limited to this.
Embodiment 1
(1) 1-(4-benzyloxy-2,6-difluoro) synthesis of phenyl-4,4-difiuorocyclohexyl-1-alkene (A-1)
In the there-necked flask of 1000 milliliters of clean dried, add 0.10 mole of 3,5-difluoro benzyloxy phenol and 150 milliliters of tetrahydrofuran (THF)s, be cooled to-70 DEG C under nitrogen protection, temperature control-65 ~-70 DEG C drips 0.11 mole of n-Butyl Lithium normal hexane (concentration 2.5 mol/L) solution, and temperature control reacts 1.0 hours; Temperature control-65 ~-70 DEG C, drips the solution of 0.1 mole of 4,4-difluoro-cyclohexanone (shown in patent DE4430668 method) and 50 milliliters of tetrahydrofuran (THF) compositions, drips complete temperature control and reacts process in 1 hour.Reaction solution is poured into slowly in the beaker that trash ice and 50 milliliters of concentrated hydrochloric acids are housed, acidification hydrolization, separatory after stirring, aqueous phase (50 milliliters × 2) methylbenzene extraction twice, merge organic phase, solvent evaporated.
After solvent evaporated, then add 400 milliliters of toluene and 2 grams of tosic acid, dewater 4 hours.Be down to room temperature, washing twice, steam compound 1-(4-benzyloxy-2, the 6-difluoro desolventized) phenyl-4,4-difiuorocyclohexyl-1-alkene (A-1), yield 77%.Gas phase purity 98.3%.(2) 4-(4,4-difiuorocyclohexyl) synthesis of-3,5-difluorophenols (B-1)
10 grams of A-1 are dissolved in 40 milliliters of tetrahydrofuran (THF)s, then add 0.5 gram of 5%(wherein, and palladium metal is 5%, and all the other are charcoal) palladium carbon catalyst, fill hydrogen hydrogenation under room temperature condition; Filtering catalyst, revolves and desolventizes to obtain 4-(4,4-difiuorocyclohexyl)-3,5-difluorophenols (B-1) 7.2 grams, yield 98%.Gas phase purity 98.5%.
(3) 4-[difluoro (4 '-propyl group dicyclohexyl) methoxyl group]-3,5-bis-fluoro-1-(4,4-difiuorocyclohexyl) synthesis of benzene (D-1)
There-necked flask pump drainage nitrogen twice, adds 0.27 mole of B-1, and 0.3 mole of triethylamine and 0.5 liter of methylene dichloride, pump drainage nitrogen once.Temperature control-80 ~-85 DEG C, (contemporary organic fluorine chemistry building-up reactions application experiment-Zhu Shi just drip 0.24 mole of C-1, Wu Yongming translates, method shown in 287 pages) dichloromethane solution, drip complete stirring 1 hour, 1.1 moles of hydrogen fluoride triethylamines and 1.1 moles of bromines are dripped successively in this temperature of maintenance, drip to finish and stir 1 hour again, pour in frozen water, add 0.2kg sodium bicarbonate, test pH value is 6-8, separatory, aqueous phase 0.3L × 2 dichloromethane extraction twice, merge organic phase, wash once with the 0.4L aqueous solution of 40g sodium bisulfite, 50g anhydrous magnesium sulfate stirs dry 1 hour.Be spin-dried for solvent, dehydrated alcohol recrystallization three times, obtains white crystal D-1, quantity 53 grams, gas phase purity 99.8%.
Mass spectroscopy: 532(molecular ion peak), 512(takes off a part HF), 284(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.94~1.79（m,38H），2.46~2.75(m，2H)，6.18(m，2H)。
Embodiment 2
Under nitrogen protection, there-necked flask adds the preparation method of 0.3 mole of B-1(B-1 see embodiment 1), 0.3 mole of triethylamine and 0.5 liter of methylene dichloride.Temperature control-80 ~-85 DEG C, drips the dichloromethane solution of 0.3 mole of C-8, drips Bi Fanying 1 hour, maintains this temperature and drip 1.1 moles of hydrogen fluoride triethylamines and 1.1 moles of bromines successively, drips Bi Fanying aftertreatment in 1 hour.Poured into by reaction solution in frozen water, add sodium bicarbonate and adjust pH for neutral, separatory, aqueous phase 0.3L × 2 dichloromethane extraction twice, merge organic phase, wash once with the 0.4L aqueous solution of 40g sodium bisulfite, and 50g anhydrous magnesium sulfate stirs dry 1 hour.Be spin-dried for solvent, dehydrated alcohol recrystallization three times, obtains white crystal D-8, gas phase purity 99.6%.
Mass spectroscopy: 612(molecular ion peak), 592(loses 1 HF), 364(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.92（m，20H）,2.68~4.91(m，4H)，6.15~7.46（m，8H）。
Embodiment 3-8
The preparation method same by embodiment 1 and 2 can synthesize:
Mass spectroscopy: 504(molecular ion peak), 484(loses 1 HF), 256(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.78（m，34H）,2.45~2.75(m，2H)，6.15~6.20（m，2H）。
Mass spectroscopy: 528(molecular ion peak), 508(loses 1 HF), 280(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.78（m，13H）,2.51~2.75(m，3H)，6.15~7.46（m，8H）。
Mass spectroscopy: 556(molecular ion peak), 536(loses 1 HF), 308(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.93~1.78（m，17H）,2.53~2.75(m，3H)，6.16~7.45（m，8H）。
Mass spectroscopy: 622(molecular ion peak), 602(loses 1 HF), 374(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.93~1.78（m，13H）,2.53~2.75(m，3H)，6.16~7.45（m，11H）。
Mass spectroscopy: 650(molecular ion peak), 630(loses 1 HF), 402(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.93~1.78（m，17H）,2.53~2.75(m，3H)，6.16~7.45（m，11H）。
Mass spectroscopy: 598(molecular ion peak), 578(loses 1 HF), 350(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.93~1.91（m，18H）,2.70~4.92(m，4H)，6.15~7.44（m，8H）。
Embodiment 9
(1) the fluoro-1-(4-difluorocyclohex-3-thiazolinyl of 4-[difluoro (4 '-propyl group dicyclohexyl) methoxyl group]-3,5-bis-) synthesis of benzene (E-1)
There-necked flask pump drainage nitrogen twice, adds prepared by 0.024 mole of D-1(embodiment 1), 0.020 mole of potassium tert.-butoxide and 0.1 liter of tetrahydrofuran (THF), be heated to 50 DEG C, temperature control 50 ~ 55 DEG C reaction 10 hours.Be chilled to room temperature, reaction solution poured into slowly in the beaker that trash ice and 10 milliliters of concentrated hydrochloric acids are housed, acidification hydrolization, separatory after stirring, aqueous phase (50 milliliters × 2) methylbenzene extraction twice, merge organic phase, solvent evaporated.Be spin-dried for solvent, dehydrated alcohol recrystallization three times, obtains white crystal E-1, quantity 7.4 grams, gas phase purity 99.8%.
Mass spectroscopy: 512(molecular ion peak), 284(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.98(m，34H),2.21~2.95(m，4H),5.20(m，1H)，6.20（m，2H）。
Embodiment 10
There-necked flask pump drainage nitrogen twice, adds prepared by 0.02 mole of D-8(embodiment 2), 0.020 mole of potassium tert.-butoxide and 0.1 liter of tetrahydrofuran (THF), be heated to 50 DEG C, temperature control 50 ~ 55 DEG C reaction 8 hours.Be chilled to room temperature, reaction solution is poured into slowly in the beaker that trash ice and 10 milliliters of concentrated hydrochloric acids are housed, acidification hydrolization, separatory after stirring, aqueous phase (50 milliliters × 2) methylbenzene extraction twice, merges organic phase, be spin-dried for solvent, dehydrated alcohol recrystallization three times, obtains white crystal E-8, gas phase purity 99.8%.
Mass spectroscopy: 592(molecular ion peak), 364(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.98（m，16H），2.22~5.20(m，7H)，6.15~7.43（m，8H）。
Embodiment 11-16
With the liquid crystalline cpd of embodiment 3-8 gained, synthesize other compounds by the method that embodiment 9 and 10 is same respectively.
Mass spectroscopy: 484(molecular ion peak), 256(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.99（m，30H）,2.21~2.95(m，4H)，5.16~5.21（m,1H）6.15~6.20（m，2H）。
Mass spectroscopy: 508(molecular ion peak), 280(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.99（m，9H）,2.21~2.95(m，5H)，5.16~5.21（m,1H）6.15~7.45（m，8H）。
Mass spectroscopy: 536(molecular ion peak), 308(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.99（m，13H）,2.21~2.95(m，5H)，5.16~5.21（m,1H）6.15~7.45（m，8H）。
Mass spectroscopy: 602(molecular ion peak), 374(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.99（m，9H）,2.21~2.95(m，5H)，5.16~5.21（m,1H）6.15~7.45（m，11H）。
Mass spectroscopy: 630(molecular ion peak), 402(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.99（m，13H）,2.21~2.95(m，5H)，5.16~5.21（m,1H）6.15~7.45（m，11H）。
Mass spectroscopy: 578(molecular ion peak), 350(methoxyl group bridged bond ruptures);
1HNMR(CDCl
3,300MHz)δH:0.95~1.99（m，14H）,2.21~4.91(m，6H)，5.16~5.21（m,1H）6.15~7.45（m，8H）。
Though all compounds that the non-limit of the present invention is claimed and preparation method thereof; but what those skilled in the art will envision that is; on published above-described embodiment basis, the professional general knowledge only in conjunction with self can obtain other similar compounds and not need to pay creative work with similar reaction scheme.Herein because length limit, only enumerate representational embodiment.
Embodiment 17 liquid-crystal composition
The liquid-crystal composition that the present embodiment is claimed, containing the D1 of 1%, other components can be selected according to practical situation.Concrete compositional selecting and consumption thereof are defined as those skilled in the art and grasp, and conventional selectable components comprises and is but not limited to following structure:
deng.
Embodiment 18 liquid-crystal composition
The liquid-crystal composition that the present embodiment is claimed, the D1 containing 5%, the D3 of 16%, 8% D7, other components can be selected according to practical situation.
Embodiment 19 liquid-crystal composition
The liquid-crystal composition that the present embodiment is claimed, containing the E1 of the 1% and E3 of 4%, other components can be selected according to practical situation.
Embodiment 20 liquid-crystal composition
The liquid-crystal composition that the present embodiment is claimed, the D1 containing 5%, the D3 of 15%, the D5 of 16% and the D7 of 14%, other components can be selected according to practical situation.
Embodiment 21 liquid-crystal composition
The liquid-crystal composition that the present embodiment is claimed, the E5 of the E1 containing 6%, the E2 of 14%, the E3 of 22% and the E4 of 18% and 10%, other components can be selected according to practical situation.
Embodiment 22 liquid-crystal composition
The liquid-crystal composition that the present embodiment is claimed, the D2 containing 8%, the D3 of 6%, the D5 of 3%, the D7 of 6%, other components can be selected according to practical situation.
Embodiment 23 liquid-crystal composition
The liquid-crystal composition that the present embodiment is claimed, containing the E2 of 8%, the E5 of the E3 of 6% and 3% and the E7 of 6%, other components can be selected according to practical situation.
Test example 1
The liquid crystal monomer used in following composition is all provided by Beijing Bayi Space LCD Materials Technology Co., Ltd..Except specified otherwise, in embodiment, the content of each component all represents mass percent.
In the present invention, each performance test parameter shorthand is as follows:
△ n is optical anisotropy, n
ofor specific refractory power (589nm, 20 DEG C);
V
thfor threshold voltage, be the character voltage (V, 20 DEG C) when transmitance is 90%, V
satfor saturation voltage, be character voltage when transmitance is 10% (V, 20 DEG C); Liquid crystal comprehensive parameter tester EOT-5016.The polaroid that setting polarizing axis is orthogonal, is attached to testing cassete (4.0 μm) top and bottom being marked with liquid crystal by polaroid.To liquid crystal cell making alive, the voltage when light is reduced to 10% transmitance from the original state of full impregnated is saturation voltage.Light source is halogen light, and the square wave of liquid crystal cell 64HZ drives.
C.p is the clearing point (DEG C) of liquid-crystal composition;
τ on is that τ off is that τ is the τ on+ τ off(time of response until reach time when transmitance 10% is cut off until time when reaching transmitance 90%) (ms).
VHR electric charge conservation rate (%): injected by mixed liquid crystal in liquid crystal cell, put into thermostat container, after temperature-stable, enters test procedure, manually gets and a little obtains electric charge conservation rate numerical value.Measuring voltage is 5V, and power-up time is 5ms, Holding Time is 500ms.
Get the liquid crystalline cpd of following parts by weight and prepare liquid-crystal composition, the performance perameter of concrete proportioning and the liquid-crystal composition of gained is by shown in following table.
There is the application of liquid crystalline cpd in TN, IPS, FFS, ADS-TFT pattern of difluoro methyl ether bridged bond and 4,4-difluorocyclohex alkane (or end has halo tetrahydrobenzene) structure, the results are shown in Table 1-table 3.
The parts by weight of each component and performance perameter in table 1, liquid-crystal composition
The parts by weight of each component and performance perameter in table 2, liquid-crystal composition
Table 3, do not add the performance perameter of the liquid-crystal composition of the compounds of this invention
As can be seen from table 1-3: the liquid-crystal composition adding the compounds of this invention, the time of response is short, Δ n numerical value is moderate, electric charge conservation rate is high, and has lower threshold voltage.The add-on of compound is advisable with 5-50%, more preferably 20-25%.
Except the composition that test example exemplifies, add other liquid-crystal compositions that other has the liquid crystalline cpd of difluoro methyl ether bridged bond and 4,4-difluorocyclohex alkane (or end has halo tetrahydrobenzene) structure provided by the invention and can obtain optical property excellent equally.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. a liquid crystalline cpd, is characterized in that, described liquid crystalline cpd is:
Wherein, R represents C
1~ C
5alkyl, wherein part CH
2group can be replaced by-C ≡ C-,-CF=CF-,-CF=CH-or-CH=CF-separately independently of one another.
2. the preparation method of liquid crystalline cpd according to claim 1, is characterized in that, comprises the steps:
(1)
through the lithium reagent that n-Butyl Lithium activation is formed, generate intermediate ethanol with 4,4-difluorocyclohex reactive ketone
dehydration of alcohols obtains compd A
(2) compd A obtains compd B through shortening
(3) compd B and corresponding salt
reaction, obtains target compound Ι;
(4) compound Ι sloughs a hydrogen fluoride under basic catalyst effect, obtains target compound II;
Wherein:
R represents C
1~ C
5alkyl, wherein part CH
2group can be replaced by-C ≡ C-,-CF=CF-,-CF=CH-or-CH=CF-separately independently of one another;
A
1, A
2represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene independently of one another, wherein Isosorbide-5-Nitrae-cyclohexylidene is not substituted or wherein 1 CH
2isosorbide-5-Nitrae-cyclohexylidene that group is replaced by Sauerstoffatom; Isosorbide-5-Nitrae-phenylene is not substituted or Isosorbide-5-Nitrae-phenylene that 1 ~ 2 hydrogen atom is replaced by fluorine atoms;
A
3represent Isosorbide-5-Nitrae-phenylene that 2 hydrogen atoms are replaced by fluorine atoms;
Z
1, Z
2represent singly-bound;
M represent 1,2 or 3, n represent 0.
3. preparation method according to claim 2, is characterized in that, in described step (1),
the mol ratio of n-Butyl Lithium and 4,4-difluoro-cyclohexanone is 1 ~ 1.1:1.1 ~ 1.5:1, and dehydration catalyst is tosic acid.
4. preparation method according to claim 2, is characterized in that, in described step (2), described shortening with palladium carbon for catalyzer, the consumption of catalyzer is 5% ~ 10% of compd A quality, under room temperature condition, carries out shortening to compd A.
5. preparation method according to claim 2, is characterized in that, in described step (3), temperature of reaction is-80 ~-85 DEG C, and the mol ratio of compd B and corresponding salt is 1 ~ 1.2:1.
6. preparation method according to claim 2, is characterized in that, in described step (4), described basic catalyst is potassium tert.-butoxide or potassium hydroxide, and the reaction times is 8 ~ 10 hours.
7. the composition containing liquid crystalline cpd according to claim 1, it is characterized in that, by weight, the consumption of described compound in liquid-crystal composition is 1 ~ 70%.
8. liquid-crystal composition according to claim 7, is characterized in that, by weight, the consumption of described compound in liquid-crystal composition is 5 ~ 50%.
9. liquid crystalline cpd according to claim 1 is manufacturing the application in display unit.
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